Process for the production of a gas of high calorific power



owER

F. DANULAT Oct. 2 5, 1938.

PROCESS FOR THE'PRODCTION OF A GAS OF HIGH CALORIFIC P Filed Jan. 2, 1935 Patented oet. 2s, 193s f Y PATENT' oFF-ICE j 2,134,548 v l.

nocnss Fon 'rim PRODUCTION oF A GAS oF man cALonmc rowEn Friedrich Dannlat, Frankfort-on-the-Main, Germany, assigner to American Lui-gi Corporation, New York, N. Y., a corporation ci.' New York Application January 2, 1935, serial Nn. 95

l In Germany January 8, 1934 1 Claim.

AThis .invention `relates to a process for the production of a gas of high calorflc-power.

It is known to produce a gas of high caloric power by the gasiilcation `oi fuels or degasication residues with oxygen and steam. In

'such case the gasiiication is carried out under a pressure of several atmospheres by mea'ns of oxygen or air enriched with oxygen, suiliciently large quantities of steam being provided in proportion to the oxygen' as to ensure that the carbon of the fuel will be converted to a preponderant extent into carbon dioxide and hydrocarbons. By this process a gas can be produced which, after the vcarbon dioxide has vbeen l5 removed, is fully comparable with normal town gas in composition, caloriic value, and burning properties. The employment of pressure enables `the synthesis of hydrocarbons (chiey methane) of high caloric power to proceed during the 20 gasification processitself, so that, after being freed from the larger quantities of carbon dioxide Vformed during the gasification process, the gas has a calorific value of, for example, 4,500 cals.

per cubic' metre and over (measured at 0 C. g5 and V760 mm. mercury gauge). The carbon monoxide content` of this gas is about the same as thatof ordinary town gas, 'and can be removed from the gas by the same processes that have been proposed for rendering town gas non- 30 poisonous, for example, by the catalytic treatment of the carbon monoxide with steam, re.

sulting in the formation of hydrogen or methane, or by condensing the carbon monoxide in a super-cooling plant for example.

If a non-poisonous gas (thatis, one that is completely free from carbon monoxide, or nearly so) is to be produced from a gas formed by blowing bituminous fuels or degasication residues with oxygen and steam, it will be necessary to n provide a plant for improving the gas, in addition 'to the producer plant and the apparatus required for the production of the oxygen (or air enriched with oxygen) that is necessary for op- ''erating the'gas producer. For this reason the 45 cost of the entire plant will be relatively. heavy,

thereby correspondingly lessening the economy of ,the production of 'a non-poisonous gas bynsaid process.

It has now been ascertained in accordance with 50 the present invention that, inmany instances,

the production of a gas of high caloriiic power by gasifying fuels under a pressure of .several atmospheres can be carried on more economically by effecting the gasification under pressure" with air, providedA the process be periormed in (cris-2oz) such a manner-by providing the gasifying medium with a sufclent content of steam, by suitably adjusting the pressure, and if necessary, preheating the gasifying medium-that considerable quantities of methane and other hydro- 5 carbon compounds are obtained from bituminousv and also non-bituminousA fuels. The methane content imparts a high calorii'lc valueto the gas, so that after the removal of carbon dioxide, steam and like substances that are eliminable 10 by condensation and by washing with water under pressure, the gas is to be regarded as approximately equal in value to water gas. If this gas, or a portion of same, be rendered non` poisonous by removing the carbon monoxide-for example by supercooling-then, in accordance with the present invention, the nitrogen, or a portion thereof, is eliminated, with thev carbon` monoxide, in the process of rendering 'the gas non-poisonous, and there is thenv obtained an innocuous gas which is at least equal to town 'gas in `caloric value and other properties. At

the same time, the poison-eliminating plant is not substantially larger andvmore expensive to run than that required for rendering town gas, or similar practically nitrogen-free gases, nonpoisonous.

In itself, the gasication of solid Ifuels with air under high pressure, such as over 3 atmospheres and more, is known. This gasiflcatlon, however,` was performed' at such high gasica- `tion temperatures that the decomposition of the condensable constituents (tars and oils) into l' permanent gases ensued. The object of that process was to generate in this manner, a gas that Was free from tar, Under such conditions, however,- 4 there is no synthetic formation of methane, without which the gascannot beraised to the necessary heating value. y

In 'carrying out the process of the present in- 40 vention, for example, air iscompressed to about 20-30 atmospheres; by a reciprocating compressor or the like, and is passed in admixture with a definite amount of highly superheated steam (for example under the same pressure) as-gasify-v 45 ing medium, into a gas producer run at the same pressure, `in which the charge of fuel (such as coke or coal) is converted into. a crude gas high in methane. After cooling the gas, and Acondensingany tars and oils thaimnay be present known methods. After chemical purification, forA 55 example with caustic soda-which serves to remove the final traces of carbon dioxide and the like from the gasthe carbon monoxide and the whole or a portion of the nitrogen are eliminated by super-cooling by knownmethods. This procedure furnishes, on the one hand, a gas which contains the methane and the heavy gaseous hydrocarbons', together with the hydrogen of the crude gas, in addition to small quantities of -carbon monoxide (as a rule not exceeding 0.5%) and a larger or smaller amount of nitrogen and thus represents a high-grade, non-poisonous gas of high calorii'lc power. There is also obtained on the other hand, a residual gas, which contains the carbon monoxide and the bulk of the nitrogen and is therefore a combustible gas, though of low quality, and can be utilized for any other convenient purposes. By working in accordancewith the present invention, practically the whole of the carbon monoxide is removed from the gas, together with so much of the nitrogen that the desired calorific value and corresponding compov sition of the gas is attained. Atthe same time, in order to control the burning properties-increase its specific' gravity for example-aportion of the previously separated carbon dioxide can be reunited with the gas.

As already mentioned, the formation of methane is effected by the application according to the' invention, of elevated pressure and copious addition of steam during the gasification. 'I'he reaction of formation of methane is exothermic and, accordingly, the amount of oxygen required for maintaining the gasifying process is small, so that thecrude gas is relatively low in nitrogen. The higher the gasification pressure the lower the nitrogen content of the gas, and for this reason, a pressure of, for example, 70-200 atmospheres may still be of particular advantage in certain cases. 'I'he increasing of the superheating temperature of the gasifying medium, prior to admission into the bed of fuel, has a similar effect on lowering the nitrogen content of the gas as the raising of the gasification pressure. The further known advantages attendant on the pressure gasification process per se, such as increased throughput, utilization of the pressure for the subsequent working stages, and so forth, are retained, since the influence of the inert nitrogen, for example ,on the throughput capacity, can be counteracted by a corresponding'increase in pressure.

The carbon monoxide fraction removed in the process of rendering the vgas non-poisonous can be employed, for example, for superheating the gasifying medium. In special cases, it may be suitable to precede the separation of the gases by supercooling by a partial catalytic treatment of. the carbon monoxideby means of steam if desired--to form methane or hydrogen, in order to reduce the loss of gas in the form of carbon monoxide, the remainder of the latter being then removed (if necessary) by supercooling.

'I'he removal, of carbon monoxide and nitrogen can also f4be effected from a portion of the gas.

' which. is then re-mixed with the remainder that has not been improved, or has been improved by other means. Alternatively, the carbon monoxide removed by supercooling or otherwise can also be treated, separately, for conversiominto methane or hydrogen by catalytic treatment and reunited to the main portion of the gas, either beforeworrafter the latter has been subjected to the separation treatment.

The following is a typical andliighly advan- 5 provided with water circulation tageous method of carrying out the process of the present invention in practice.

In gas-producer plants, situated in coal districts gasification with air and steam, under a pressure of several atmospheres, according to the invention, furnishes a gas which, after being freed from carbon dioxide, has a caloric value of about 3,000 cals. per cubic metre and contains about 8-12% of methane. This gas can be used, with advantage, as an industrial and heating gas, or also as an addition to any gases produced by the distillation of coal, lignite and the like. This gas can be transmitted, under its initial pressure, 4through distance-supply mains, to the points of consumption, where a portion is utilized as industrial and heating gas. At'the same or other points of consumption, central improving stations. may be arranged, which distribute the gas'for'household purposes, after it has been freed from carbon monoxide and a portion of its nitrogen. 'I'he separated carbon monoxide can be sent back into the industrial-gas mains. For the purpose of giving those skilled in the art a better understanding of the invention, a preferred procedure of carrying the process into practice will be described in conjunction with the laccompanying drawing, which illustrates a system of apparatus in which the present process may be conducted. I

A multistage compressor l compresses air to a pressure of about 20 to 30 atmospheres. The compressed air is conducted to a superheater 2 and is heated nto a temperature of about 500 C. Steam, preferably superheated in the lower part of heater 2 and having approximately the same temperature and pressure as the compressed and pre-heated air, is admixed to the air. The mixture of air and steam is introduced as a gasication agent into the lower part of a 'gas generator 3 being underv the same elevated pressure at which the solid fuel is gasified and produces a gas rich in methane. Conventionalgas generators may be used which are preferably provided with'sluice chambers for introducing fresh fuel and for the removal of ash. The gas produced leaves at the top of the generator 3 and is introduced into a tubular cooler I. In the cooler the gas is cooled down to about 20 to 30 C. by means of water whereby tar and oils present in the gas are condensed and separated. From the cooler 4 the cooled gas is conducted to a washing tower under pressure in which the carbon dioxide and the greater part of the hydrogen sulfide are absorbed. The water is injected into the washing tower at the top thereof and trickles down for example over earthenware rings countercurrent to the gas which is introduced at the bottom of the tower and streams upward. After the water has absorbed the carbon dioxide and the hydrogen sulfide from the gas it is conducted into a tank l and is relieved from pressure whereby it will release the substancesl absorbed in the Washing tower 5, particularly carbon dioxide and hydrogen sulfide. The water is again brought to the initial pressure by means of centrifugal pump 1 and is re-circulated through the tower 5 and tank 6. The gases separated from the circulating water leave the tank 6 through conduits I2 and may be subjectedto treatments by a conventional apparatus for separating the carbon dioxide from the hydrogen sulfide which may be utilized lin any the art will readily understand, elements' 2 to Q animas `freed from carbon dioxide and hydrogen sulfide is introduced to the purier 8 inlwhich the last traces of carbon dioxide are eliminated by means of .caustic soda. In the adjoining separator 9. the carbon monoxide and a portion of the nitrogen are eliminated from the 'gas so that a nonpoisonous gas is produced which is practically free from carbon monoxide which .has ahigh caloric power and which has the quality of town gas. The separated gas constituted principally of carbon monoxide and nitrogen may be used. for example, for heating the superheater 2 by burner 24, but it may also be converted intohydrogen and methane by one of the conventional catalytic processes and reintroduced `into the gas circulation. This reintroduction may be before the washing tower 5 or the purifier 8, butin case thejgas is practically free from carbon monoxide it can be directly introduced into the gasoineter Il and added to the gas free from carbon monoxide supplied by the separator 9. Conduits I4, I5,v I6, I1, I8, `I9 and 20 are provided in order to regulate the flow of the carbon monoxide and nitrogen which may be adjusted at will by means of valves associated with said conduits. 'From' gasometer il the non-poisonousvand puriiied .town gas is introduced into'the mains and distributed to the consumers.

The purifier 0, separator 9, the apparatus I0 for the conversion of the separated carbon monoxide into hydrogen and'methane and the gasometer Il may be provided at the same place where the gas generator 3 and its auxiliary apparatus compressor vl, superheater 2, cooler 4 and washing tower 5 vare located. It is also possible, hovrever, to separate the two-groups of apparatus from each other and to connect them by means of long-distance mains. In case only a portion of the generated gas is subjected to the separation treatment and the rest is utilized without eliminating the poisonous constituents or is added to the portion freed from poisonous gases,

conduits 22 are branched off from the main flow pounds are completely removed without additional expense.

Moreovenln the process of the present invention, the actual gasifying'opeation proceeds in a more advantageous manner, and freer from trouble, than in the known processes in which oxygen vand steam are employed as gasifying' media and the gasification is performed under a pressure of several atmospheres, (which known process will hereinafter be referred toV by the abbreviated term "oxygen gasication"), because the air compressor is substantially more reliable in. operation than the oxygencompressor, and, owing to the cooling action of the inert nitrogen,

the risk of clinkering in the gas producer-a highly important factor in oxygen gasificationis substantially less imminent than is possible in oxygen gasification, through the increase in the already very high steam-saturation of the gasifying medium.

The present invention completely abolishes the risk of any sudden burning of pressure-supporting structural materials (such as iron, and the like) situated in the gas producer, such as may occur, in oxygen gasificationunless reliably prevented by special constructional measuresof gas in the apparatus preferably in the conduit 2| connecting the Washing tower to purifier 8, f

or in asuitable part of the-long-distance gas mains. Through'conduit 23 the gas eliminated in the separator 9 and principally constituted of carbon monoxide and nitrogen may be added to the portion of the generated gas which is utilized in an untreated condition. As those skilled Y in of the apparatus and if necessary element I0, are under the same elevated pressure.

The process of the present invention exhibits with the aid of oxygen is dispensed with.

By means of a practically negligible enlargement of the gas separating plant, the nitrogen' entering the gas with the gasifying air is removed at the same time as the carbon monoxide,

whereas, in the known gasication of fuels with oxygen and steam under pressure, two gas-se 1- arating plants of approximately equal dimensio is were required--one for the gas and the other for the air.. l

Simultaneously with the separating treatment,

water, naphthalene' and organic sulphur comin the'event of a sudden cessation of the supply of the steam added to the oxygen employed as the gasifying medium.

Finally, in the process of the present invention, less importance attaches to the losses of gasifying medium or crude gassuch as are liable to happen in any processof pressure gasification and, to some extent, even in charging and discharging fuel and ash intoand from the producer-than in the case of oxygen gasication, in which the gasifying medium and also the crude gas are more expensive to produce.l Consequently, the process of thepresent invention constitutes an important improvement over the known processes for the production of a non- Per cent CO2--- 22.8 HzS 1.4 CnHm 0.7 O2 0.1 Hz 23.1 CO 11.7 CHi. 11.3 N2 28.9

This .gas is almost conpletely freed from carbon dioxide and sulphuretted hydrogen by water in' a pressure washer, and then has the composi- I -tionz- Per cent CnHm 0.9 Oz 0.1 CO 15.4 H2 30.5 CH.. 14.9 Nz 38.2

The caloriiic value is about 3,000 cal. per cubic metre.

On passing this gas through a separation plant thereby removing the carbon monoxide and the nitrogen, to a certain extent, a. non-poisonous town gas, having the following composition is obtained:

The maximum calorc value o1' this gas is about 4,450 cal. per cubic metre.

The process of producing a non-poisonous gas of high calorlc power which comprises gasifying a. solid carbonaceous fuel under a pressure in excess of twenty atmospheres with a. gasifying agent consisting of air and steam in such proportions that about 1 part by volume of airis present for about 1.6 parts by volume of steam whereby substantial quantities of methane are produced, and subsequently supercooling the resulting crude gas to eliminate the carbon monoxide and at least part or the nitrogen therefrom.

FRIEDRICH DANUmT. 

